CN107240663A - A kind of polymer coating barrier film and preparation method thereof - Google Patents
A kind of polymer coating barrier film and preparation method thereof Download PDFInfo
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- CN107240663A CN107240663A CN201710299391.5A CN201710299391A CN107240663A CN 107240663 A CN107240663 A CN 107240663A CN 201710299391 A CN201710299391 A CN 201710299391A CN 107240663 A CN107240663 A CN 107240663A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of polymer coating barrier film and preparation method thereof, the polymer coating that the polymer coating barrier film is formed by polyolefin micro porous polyolefin membrane and the polymer coating slurry being coated on polyolefin micro porous polyolefin membrane is constituted；Polymer coating slurry is made up of the raw material of following mass parts：100 parts of main polymers, 10~30 parts of auxiliary polyalcohols, 300~900 parts of mixed solvents, 5~20 parts of pore-foaming agents and 3~10 parts of surfactants.Mixed solvent of the Inventive polymers coating paste as a result of auxiliary polyalcohol and containing ionic liquid so that polymer coating Stability of Slurry is strong, polymer coating adhesive force is strong, it is easy to fall off not allow；Its production is not interfered with yet even if placing to reuse after 72h, is reused after placement 48h and does not interfere with properties of product yet, the polymer coating assigns the functions such as the heat-resisting, lyophily of composite diaphragm, improve the security performance and ion permeability of barrier film.
Description
Technical field
The present invention relates to lithium ion battery separator technical field, more particularly to a kind of polymer coating barrier film and its preparation side
Method.
Background technology
Because lithium ion battery has the advantages that high operating voltage, energy density height, memory-less effect and has extended cycle life,
It is widely used to the fields such as portable digital equipment, electric tool and electric automobile at present.
Barrier film is an indispensable part in lithium ion battery, and its main function is that both positive and negative polarity isolation is prevented into straight
Contact and it is short-circuit, while permission electrolyte in ion can pass freely through.The performance of barrier film can influence battery internal resistance and
Cell interface structure, thus influence the energy of lithium ion battery to export, power output and cycle life etc..Therefore, lithium-ion electric
Pond barrier film should have good electronic isolation, heat-resistant stability, electrolyte wetability and chemical stability etc..
The commercialization barrier film of current main-stream is polyolefin-based separator, such as microporous polypropylene membrane, polyethene microporous membrane and poly-
Ethylene/polypropylene composite multi-layer microporous barrier.Due to the inherent attribute of the materials such as polypropylene and polyethylene, polyalkene diaphragm is relatively low
At a temperature of have good chemical stability and mechanical strength；But the fusing point of polyalkene diaphragm is relatively low, in the higher feelings of temperature
Under shape, MIcroporous polyolefin film meeting extensive shrinkage causes battery short circuit and triggers thermal runaway, causes batteries caught fire or even blast.This
Outside, MIcroporous polyolefin film is good to electrolyte wetability, electrolyte absorption and retention is weaker, so as to there is larger electrolysis
Liquid disclosure risk, while influenceing battery cycle charge-discharge performance and cycle life etc..
The coating for carrying out inorganic particulate to MIcroporous polyolefin film using blade coating or rotogravure application can relatively significantly improve
The heat resistance of barrier film, but be due to the reason that particle diameter is smaller, specific surface area is larger of inorganic particulate, inorganic particulate is easily rolled into a ball
Poly-, coating uniformity is poor；And the adhesiveness of inorganic particulate coating and MIcroporous polyolefin film is not good, there is obvious inorganic grain
Sub- obscission.Therefore, inorganic particulate coating is carried out to polyolefin to improving membrane properties limitation.
The higher polymer-coated of fusing point can also be improved into barrier film to a certain extent on the surface of MIcroporous polyolefin film
Electrolyte wetability and heat-resistant stability.Kynoar or vinylidene fluoride-hexafluoropropylene copolymer are coated in polyolefin
Surface, although enhance the heat resistance and electrolyte absorbability of barrier film to a certain degree.But Kynoar, inclined fluorine second
The fusing point of alkene-hexafluoropropylene copolymer is relatively low, therefore heat resistance improves unobvious, is unsuitable for being used for electrokinetic cell.
Now by the heat resistant type polymer-coated such as polyimides, polyether-ketone and aromatic polyamide in polyolefin micropore
The document patent report of film.CN105336901A provides a kind of preparation method of coating barrier film between high-performance hole, i.e., by resistance to height
Warm polymer is configured to low concentration oil system slurry, to be exerted into the form of dip-coating on basement membrane, this mode do not increase membrane thicknesses,
It is simple to operate, but the dissolubility due to such heat-resistant polymer in the solvent is poor, and oil is that the stability of slurry is poor, multiple
Close the phenomenon that barrier film has dry linting so that the improvement of heat resistance is not obvious.CN103531736A is resistance to by aromatic polyamide etc.
Thermal fiber is configured to slurry, prepares refractory coating by coating, pre- pore-creating, solidification, washing and dry step, although this method
The fusing-off temperature of barrier film can be caused to be higher than 210 DEG C, but this method complex steps, time-consuming, it is quick big to be unfavorable for industrialization
Large-scale production, while slurry is also not sufficiently stable.
The content of the invention
In order to overcome the deficiencies in the prior art, first purpose of the invention be to provide one kind easily prepare, body
Be the good polymer coating slurry of stability and containing the polymer coating by the polymer coating sizing material forming it is compound every
Film.Polymer coating slurry employs auxiliary polyalcohol and the mixed solvent containing ionic liquid so that polymer coating slurry
Stability is strong, and polymer coating adhesive force is strong, it is easy to fall off not allow.The polymer that this is easily prepared, system stability is good is applied
After layer slurry preparation, its production is not interfered with even if placing to reuse after 72h, is reused after placement 48h and does not interfere with production yet yet
Moral character energy, greatly facilitates production and manages.The polymer coating slurry is coated on polyolefin micro porous polyolefin membrane, forms poly-
Compound coating, the polymer coating is easily molded, it is easy to fall off not allow.
Second object of the present invention is to provide a kind of preparation method of composite diaphragm, prepared by the composite diaphragm provided
Method is simple to operation, pore-creating is uniform sequential, cost is low, be easy to large-scale production.Composite diaphragm obtained by this method has
The features such as Good Heat-resistance, good electrolyte affinity.The lithium ion battery prepared using the composite diaphragm has outstanding
Security performance and cycle performance.
First purpose of the present invention adopts the following technical scheme that realization：
A kind of polymer coating barrier film, is applied by polyolefin micro porous polyolefin membrane and the polymer being coated on polyolefin micro porous polyolefin membrane
The polymer coating composition that layer slurry is formed.The polymer coating slurry is made up of the raw material of following mass parts：100 parts of masters
Body polymer, 10~30 parts of auxiliary polyalcohols, 300~900 parts of mixed solvents, 5~20 parts of pore-foaming agents and 3~10 parts of surface-actives
Agent.Mixed solvent as a result of auxiliary polyalcohol and containing ionic liquid so that polymer coating Stability of Slurry is strong, gathers
Compound coating adhesion is strong, it is easy to fall off not allow.The polymer coating assigns the functions such as the heat-resisting, lyophily of composite diaphragm, improves barrier film
Security performance and ion permeability.
Further, the main polymer be polyacrylonitrile, it is PEI, poly, poly-
One or more kinds of compositions in the derivative blending of ether sulfone, polyarylsulfone (PAS) and above-mentioned polymer, copolymerization system.
Further, the weight average molecular weight Mw of the main polymer is 2 × 104≤Mw≤2.4×105, and molecular weight point
Cloth meets 1.5≤Mw/Mn≤10, and wherein Mn is number-average molecular weight.The main polymer that the present invention is selected within the range when, gather
Compound coating paste has suitable coating viscosity, and coating has preferable pore-forming effect and surface density.Weight average molecular weight is too low,
Pore-forming effect is poor；Weight average molecular weight is too high, and coating weight increase is larger, and polymer-coated fluid viscosity is excessive, is unfavorable for
The coating of coating is uniform.There is the polymer of selection glass transition temperature or fusing point to be more than 180 DEG C, in load-less condition
Under, heat-resisting operating temperature is more than 180 DEG C.
Further, the auxiliary polyalcohol is Kynoar, vinylidene fluoride-hexafluoropropylene copolymer and poly- methyl-prop
One or more kinds of compositions in e pioic acid methyl ester.The present invention shares solvent from auxiliary polyalcohol with main polymer, with viscous
Knot property and the property for forming micropore, so that it is guaranteed that main polymer is not fallen off, while the permeability of composite diaphragm can be avoided
With porosity degradation.The auxiliary polyalcohol has affinity to electrolyte, while there is certain gelatinisation ability, from
And it is even closer to cause barrier film to be fitted with pole piece, accelerate the injection process of battery assembling.
Further, the mixed solvent is the mixing liquid of organic solvent and ionic liquid, in the mixed solvent ionic liquid
The mass fraction of body is 3%~20%, and surplus is organic solvent.The mass fraction of ionic liquid is preferably 5~20%, further
Preferably 5%~15%.The mass fraction of ionic liquid is less than 3%, then mixed solvent can not substantially ensure that the steady of slurry system
It is qualitative；Mass fraction is higher than 20%, then is difficult to ensure that follow-up fully washing removes remaining mixed solvent.It is used alone organic molten
Agent is difficult to dissolve to main polymer, it is difficult to prepare the solution of higher concentration, so that cause consumption of organic solvent big, and
It is difficult to obtain the solution of homogeneous stability.The present invention is made in itself using organic solvent and the mixed solvent of ionic liquid, ionic liquid
For a kind of " green " solvent, polymer can be dissolved to a certain degree, at the same ionic liquid can as polymer plasticizer, with
Polymer has the complexing of chemical bond, so as to strengthen the solvability of organic solvent, so as to be easier to obtain preferable coating
Slurry.
Further, the organic solvent is DMF, DMA, N- crassitudes
One or more kinds of compositions in ketone, acetone and ethanol；The ionic liquid is 1- butyl -3- methyl imidazolium tetrafluoroborates
([BMIM]BF4), 1- methyl -3- butyl imidazoles trifluoroacetates ([BMIM] CF3CO2), 1- butyl -3- methylimidazole villaumites
([BMIM] Cl), 1- butyl -3- methylimidazoles hexafluorophosphates ([BMIM] PF6), 1- vinyl -3- ethyl imidazol(e) tetrafluoro boric acids
Salt ([VEIm] BF4), double (fluoroform sulphonyl) inferior amine salt ([EMIM] NTF of 1- ethyl-3-methylimidazoles2), 1- ethyl -3- first
Base imidazolium chloroaluminate ([EMIM] AlCl4), 1- benzyl -3- methylimidazole villaumites ([PhCH2MIm] Cl), 1- nitrile propyl group -3- first
Double (fluoroform sulphonyl) inferior amine salt ([CPMIm] NTf of base imidazoles2) in one or more kinds of combinations.
Further, the pore-foaming agent is in polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and gamma-butyrolacton
One or more composition.In the case of no addition pore-foaming agent, coating is in poration process, and a part forms strip
Finger-like macropore, weakens the mechanical performance of coating；A part but forms the structure of densification, influences the porosity and gas permeability of coating
Energy.The pore-foaming agent that the present invention is selected can suppress the formation of finger-like macropore and compact texture layer, promote cellular or network-like micro-
The formation of pore structure, increases the quantity of micropore, be conducive to the crosslinking intercommunication between Kong Yukong and increase coating lyophily and
Liquid-keeping property.Pore-foaming agent not only to main polymer, also has drilling effect to auxiliary polyalcohol.
Under mixed solvent, pore-foaming agent and surfactant three's collective effect, Inventive polymers coating paste system
It is stable, there is certain wetability to MIcroporous polyolefin film, so as to improve the uniformity and stability of coating.
Further, the surfactant is in polysorbas20, polysorbate40, polysorbate60, Tween61, Tween 80, polysorbate85
One or more kinds of compositions.The surfactant that the present invention is selected is nonionic surface active agent, and they can significantly change
The interfacial property become between polymer solution and steam or coagulating bath liquid, the parent for improving solvent and steam or coagulating bath liquid
With power so as to help agent polymer pore-forming, promote the formation of macropore, so as to avoid the micropore Severe blockage of basement membrane from causing
Porosity significantly declines.In addition the speed that can accelerate to be separated of surfactant is added so that coating liquid can be quick
It is solidificated on basement membrane.
The second object of the present invention is to provide a kind of preparation method of polymer coating barrier film, including
Prepare polymer coating slurry：
Main polymer and auxiliary polyalcohol are added in the mixed solvent and are heated to stirring and dissolving, after the completion of dissolving, plus
Enter pore-foaming agent, surfactant, continue heating stirring to being completely dissolved, 0.5~3h of cooling and standings；Heating stirring temperature be 50~
120℃；
Prepare composite diaphragm：
The above-mentioned polymer coating slurry prepared is coated on MIcroporous polyolefin film surface, pore-creating, cleaned, dried, obtain
To the composite diaphragm.
Further, the coating method is one kind in dip-coating, blade coating, slit, nick and inverse roller；The pore-creating technique
For one kind in spirogram method, coagulating bath；It is of the invention preferential using spirogram method.It is described dry using natural air drying, hot blast baking
One kind in dry, high temperature drying, the present invention is preferential to use hot-air seasoning, and drying temperature is 60~80 DEG C.
Compared with prior art, the beneficial effects of the present invention are：
(1) mixed solvent of the Inventive polymers coating paste as a result of auxiliary polyalcohol and containing ionic liquid,
So that polymer coating Stability of Slurry is strong, polymer coating adhesive force is strong, it is easy to fall off not allow；Even if being reused after placing 72h
Do not interfere with to reuse after its production, placement 48h and do not interfere with properties of product yet, Inventive polymers coating paste is easily made yet
It is standby obtain, system stability it is good, greatly facilitate production and manage.The polymer coating assigns heat-resisting, lyophily of composite diaphragm etc.
Function, improves the security performance and ion permeability of barrier film；
(2) main polymer heat resisting temperature of the present invention be more than 180 DEG C, and polymer coating do not allow it is easy to fall off；Therefore can
To significantly improve the heat-resistant stability of barrier film, strengthen the security performance of lithium ion battery.Auxiliary polyalcohol has to electrolyte
Affinity, while have certain gelatinisation ability, so that barrier film is fitted even closer with pole piece, accelerates battery assembling
Injection process.The present invention is shared from auxiliary polyalcohol with main polymer, with caking property and the property for forming micropore, so that
Ensure that main polymer is not fallen off, while the permeability and porosity degradation of composite diaphragm can be avoided；
(3) the electrolyte wetability and electrolyte of the composite diaphragm prepared by the present invention absorb reserve capability and improved,
So that the lithium ion battery of composite membrane as the barrier film prepared using the present invention has more preferably cycle charge discharge electrical property and cycle life；
(4) composite diaphragm preparation method provided by the present invention is simple to operation, pore-creating is uniform sequential, cost is low, be easy to
Large-scale production.
Brief description of the drawings
Fig. 1 is the ESEM surface topography photo of 5,000 times of the amplification of the composite diaphragm prepared by embodiment 1；
Fig. 2 is the ESEM surface topography photo of 10,000 times of the amplification of the composite diaphragm prepared by embodiment 1.
Embodiment
Below, with reference to accompanying drawing and embodiment, the present invention is described further, it is necessary to which explanation is, not
Under the premise of afoul, new implementation can be formed between various embodiments described below or between each technical characteristic in any combination
Example.
In the present invention, if not refering in particular to, all part, percentage are unit of weight, equipment and raw material for being used etc.
It is commercially available or commonly used in the art.Method in following embodiments, is the normal of this area unless otherwise instructed
Rule method.
Embodiment 1
A kind of polymer coating barrier film prepared by the following method
(1) it is 1.2 × 10 by 10g weight average molecular weight Mw5, molecular weight distribution mw/mn it is poly- for 2 PEI and 1.6g
Vinylidene is added to by 55g DMAC N,N' dimethyl acetamides and 6.5g ionic liquids [BMIM] BF4The in the mixed solvent of composition,
In 80 DEG C of stirring and dissolvings.Add 1.3g polyethylene glycol, 0.6g Tween 80s after the completion of dissolving, continue heating stirring to completely molten
Solution, cooling and standings 1h.
(2) coating liquid configured is coated in the bilateral of polyethene microporous membrane, be placed on temperature be 60 DEG C, humidity be
5min uses spirogram method pore-creating in 80% climatic chamber, is cleaned with deionized water, finally the hot blast by barrier film at 75 DEG C
Middle drying is to composite diaphragm.
Comparative example 1
Using with identical polyethene microporous membrane in embodiment 1 as a comparison case, without any processing.
Embodiment 2
A kind of polymer coating barrier film prepared by the following method
(1) it is 8 × 10 by 10g weight average molecular weight Mw4, molecular weight distribution mw/mn for 4 polyacrylonitrile and the inclined fluorine second of 2g
Alkene-hexafluoropropylene copolymer is added to by 40g N,N-dimethylformamides and 4.5g ionic liquids [EMIM] AlCl4Composition
In the mixed solvent, in 70 DEG C of stirring and dissolvings.1.5g polyvinylpyrrolidones, 0.4g polysorbate60s are added after the completion of dissolving, is continued
Heating stirring is to being completely dissolved, cooling and standings 1.5h.
(2) coating liquid configured is placed to the bilateral that microporous polypropylene membrane is coated in after 24h, made using spirogram method
Hole, that is, be placed on pore-creating 4min in the climatic chamber that temperature is 65 DEG C, humidity is 85%, cleaned with deionized water, then will
Barrier film in 80 DEG C of hot blast drying to composite diaphragm.
Comparative example 2
Make mixed solvent into 40g DMF single composition organic solvents as different from Example 2, no
Use 1.5g polyvinylpyrrolidones.Remaining is same as Example 2.
Embodiment 3
A kind of polymer coating barrier film prepared by the following method
(1) it is 8 × 10 by 10g weight average molecular weight Mw4, molecular weight distribution mw/mn be 2 poly
70g 1-METHYLPYRROLIDONEs and 6.5g ionic liquids [CPMIm] NTf are added to 2g Kynoar2In the mixed solvent,
In 80 DEG C of stirring and dissolvings.Add 1g polyvinylpyrrolidones, 0.5g polysorbate60s after the completion of dissolving, continue heating stirring to complete
Dissolving, cooling and standings 1h.
(2) coating liquid configured is coated in the bilateral of polyethene microporous membrane, using spirogram method pore-creating, that is, is placed on
5min in the climatic chamber that temperature is 60 DEG C, humidity is 80%, is cleaned, finally the hot blast by barrier film at 75 DEG C with deionized water
Middle drying is to composite diaphragm.
Comparative example 3
As different from Example 3 without 2g Kynoar, remaining is same as Example 3.
Embodiment 4
The coating liquid configured is coated in the bilateral of polyethene microporous membrane as different from Example 1, using coagulating bath
Pore-creating, that is, be immersed in the mixing liquid of 25 DEG C of ethanol and deionized water (volume ratio of deionized water is 85%), spend from
Sub- water washing, finally by barrier film in 75 DEG C of hot blast drying to composite diaphragm.Remaining is same as Example 1.
Embodiment 5
Step (2) will be that to make standing time into be 48h to 24h standing time as different from Example 2, remaining and embodiment
2 is identical.
Embodiment 6
Step (2) will be that to make standing time into be 72h to 24h standing time as different from Example 2, remaining and embodiment
2 is identical.
Below, barrier film its performance obtained in embodiment 1-6 and comparative example 1-3 is compared.
The performance comparison of barrier film in embodiment and comparative example that the present invention of table 1 is provided
With reference to accompanying drawing 1-2 and table 1 it can be found that Inventive polymers coating paste system stability is strong, put for a long time
Put and have no effect on production and use, greatly facilitate production and manage；Polymer coating adhesion property is good, the probability of coating dry linting
Substantially reduce；There is microporous structure by Inventive polymers coating, porosity, permeability etc. can be kept not to occur significantly
Decline；In addition, composite diaphragm has the Heat-resistant stable performance significantly increased, electrolyte wetability and absorbability are also changed
It is kind, therefore the lithium ion battery of the composite diaphragm provided using the present invention has outstanding battery safety and cyclicity
Energy.
Above-mentioned embodiment is only the preferred embodiment of the present invention, it is impossible to limit the scope of protection of the invention with this,
The change and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed scope.
Claims (10)
1. a kind of polymer coating barrier film, it is characterised in that by polyolefin micro porous polyolefin membrane and be coated on polyolefin micro porous polyolefin membrane
Polymer coating slurry formed polymer coating composition；The polymer coating slurry by following mass parts raw material group
Into：100 parts of main polymers, 10~30 parts of auxiliary polyalcohols, 300~900 parts of mixed solvents, 5~20 parts of pore-foaming agents and 3~10
Part surfactant.
2. polymer coating barrier film according to claim 1, it is characterised in that the main polymer be polyacrylonitrile,
The derivative blending of PEI, poly, polyether sulfone, polyarylsulfone (PAS) and above-mentioned polymer, copolymerization system
In one or more kinds of compositions.
3. polymer coating barrier film according to claim 2, it is characterised in that the weight average molecular weight of the main polymer
Mw is 2 × 104≤Mw≤2.4×105, and molecular weight distribution meets 1.5≤Mw/Mn≤10, wherein Mn is number-average molecular weight.
4. polymer coating barrier film according to claim 1, it is characterised in that the auxiliary polyalcohol is polyvinylidene fluoride
One or more kinds of compositions in alkene, vinylidene fluoride-hexafluoropropylene copolymer and polymethyl methacrylate.
5. polymer coating barrier film according to claim 1, it is characterised in that the mixed solvent be organic solvent and from
The mixing liquid of sub- liquid, the mass fraction of in the mixed solvent ionic liquid is 3%~20%, and surplus is organic solvent.
6. polymer coating barrier film according to claim 5, it is characterised in that the organic solvent is N, N- dimethyl methyls
One or more kinds of compositions in acid amides, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, acetone and ethanol；The ion
Liquid is 1- butyl -3- methyl imidazolium tetrafluoroborates, 1- methyl -3- butyl imidazoles trifluoroacetate, 1- butyl -3- methyl miaows
Azoles villaumite, 1- butyl -3- methylimidazoles hexafluorophosphate, 1- vinyl -3- ethyl imidazol(e)s tetrafluoroborate, 1- ethyl -3- first
Double (fluoroform sulphonyl) inferior amine salts of base imidazoles, 1- ethyl-3-methylimidazoles chloro-aluminate, 1- benzyl -3- methylimidazole villaumites,
One or more kinds of combinations in double (fluoroform sulphonyl) inferior amine salts of 1- nitrile propyl group -3- methylimidazoles.
7. polymer coating barrier film according to claim 1, it is characterised in that the pore-foaming agent is polyvinylpyrrolidine
One or more kinds of compositions in ketone, polyethylene glycol, polyvinyl alcohol and gamma-butyrolacton.
8. polymer coating barrier film according to claim 1, it is characterised in that the surfactant is polysorbas20, told
One or more kinds of compositions in temperature 40, polysorbate60, Tween61, Tween 80, polysorbate85.
9. a kind of preparation method of polymer coating barrier film, it is characterised in that including
The step of preparing polymer coating slurry：
Main polymer and auxiliary polyalcohol are added in the mixed solvent and are heated to stirring and dissolving, after the completion of dissolving, adds and causes
Hole agent, surfactant, continue heating stirring to being completely dissolved, 0.5~3h of cooling and standings；Heating stirring temperature is 50~120
℃；
The step of preparing composite diaphragm：
The above-mentioned polymer coating slurry prepared is coated on MIcroporous polyolefin film surface, pore-creating, cleaned, dried, obtain institute
State composite diaphragm.
10. the preparation method of polymer coating barrier film according to claim 9, it is characterised in that the coating method is
One kind in dip-coating, blade coating, slit, nick and inverse roller；The pore-creating technique is one kind in spirogram method, coagulating bath；It is described
Dry using one kind in natural air drying, hot-air seasoning, high temperature drying, drying temperature is 60~80 DEG C.
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| CN110635090A (en) * | 2019-09-27 | 2019-12-31 | 宁德卓高新材料科技有限公司 | Preparation method of high-heat-resistance vinylidene fluoride polymer mixed coating diaphragm |
| CN112321860A (en) * | 2020-10-29 | 2021-02-05 | 深圳市华科创智技术有限公司 | Preparation method of bending-resistant microporous film and prepared microporous film |
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| CN113937417A (en) * | 2021-10-27 | 2022-01-14 | 长园泽晖新能源材料研究院(珠海)有限公司 | Photocuring modified lithium ion battery diaphragm and preparation method thereof |
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